Process for preparing 1(4-pentonoyl)-3,3-dimethylcyclohexane and intermediates used in a said process

ABSTRACT

A process comprising the steps of reacting 1-acetyl-3,3-dimethylcyclohexane with an alkyl acetate, thereby forming a diketone having the structure: ##STR1## reacting the said diketone with an allyl halide to form a substituted diketone having the structure: ##STR2## which is transformed into the compound having the structure: ##STR3## by means of a retro-Claisen reaction. Also described is the use in augmenting or enhancing the aroma of perfume compositions, colognes or perfumed articles of the compound having the structure: ##STR4##

This application is a continuation-in-part of application for U.S.Letters Patent, Ser. No. 375,767 filed on May 6, 1982.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 4,064,281 issued Dec. 20, 1977 and 4,102,928 issued July25, 1978 describe processes for preparing compounds defined according tothe structure: ##STR5## in low yields by reaction of an allylic halidewith acetyl-3,3-dimethycyclohexane in the presence of a phase transfercatalyst. Primarily U.S. Pat. 4,064,281 teaches the reaction: ##STR6##The compound having the structure: ##STR7## is prepared incidentally tothat reaction. Dutch Published application No. 7500838 discloses thepreparation of the compound having the structure: ##STR8## in a mannerdifferent in kind from the instant process giving rise to yields farbelow the yields produced according to the instant process and disclosesits use in perfumery and in augmenting foodstuff flavors. The perfumeryuse of this compound and other members of its class is described as"floral, green, herbaceous and chypre". The use as a galbanum componentis also disclosed therein.

Chemical compounds which can provide pineapple-like, oily-sweet, floral,fruity, woody, bark-like and green aroma nuances with minty undertonesare highly desirable in the art of perfumery. Many of the naturalmaterials which provide such fragrances and contribute such desirednuances to perfumery compositions and perfumed articles are high incost, unobtainable at times, vary in quality from one batch to anotherand/or are generally subject to the usual variations in naturalproducts.

There is, accordingly, a continuing effort to find synthetic materialswhich will replace, enhance or augment the fragrance notes provided bynatural essential oils or compositions thereof. Unfortunately, many ofthe synthetic materials either have the desired nuances only to arelatively small degree or they contribute undesirable or unwanted odorto the compositions.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the reaction product of Example Icontaining the compound having the structure: ##STR9##

FIG. 2 is the GLC profile of the distillation product of the reactionproduct of Example I for the compound defined according to thestructure: ##STR10##

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the reaction product of Example I(conditions: 6 foot ×0.25", 12% S.F.96, column programmed at 80°-220° C.per minute). The peak indicated by reference numeral "10" is the peakfor the unreacted starting material defined according to the structure:##STR11## The peak indicated by reference numeral "11" is the peak forthe desired product having the structure: ##STR12##

FIG. 2 is the GLC profiles for Fraction 18 of the distillation productof the reaction product of Example I containing the compound having thestructure: ##STR13## The peak indicated by reference numeral "20" is thepeak for the compound having the structure: ##STR14##

THE INVENTION

Our invention relates to a process for preparing a compound having thestructure: ##STR15## comprising the steps of reacting the compoundhaving the structure: ##STR16## with a lower alkyl acetate having thestructure: ##STR17## wherein R₂ is C₁₋ C₅ lower alkyl includingmethylethyl, n-propyl, i-propyl, n-butyl, 2-butyl, t-butyl and 1-pentyl,2-pentyl and the like in order to produce a diketone defined accordingto the structure: ##STR18## then reacting the resulting diketone with anallyl halide having the structure: ##STR19## wherein X is bromo or iodoin order to produce a substituted diketone having the structure:##STR20## The resulting substituted diketone having the structure:##STR21## is then reacted with an alkali metal alkoxide by means of aretro-Claisen reaction whereby the compound having the structure:##STR22## is formed directly.

Our process is embodied in the following reaction scheme: ##STR23##wherein M₁ represents alkali metal such as sodium, potassium and lithiumand C₁ -C₄ lower alkyl including methyethyl, n-propyl, i-propyl,n-butyl, i-butyl and t-butyl.

Referring to the reaction: ##STR24## R₃ may be C₁ -C₅ lower alkylincluding methylethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl,1-methyl-2-propyl and 2-methyl-2-propyl. The reaction takes place at atemperature in the range of from about 20° C. up to about 50° C. and apressure in the range of from about 0.7 atmospheres up to about 5atmospheres, preferably at a temperature of from about 30° C. up toabout 40° C. and at 1 atmosphere pressure. The reaction takes placeusing an alkali metal alkoxide catalyst such as sodium methoxide, sodiumisopropoxide, potassium methoxide and potassium isopropoxide. Inaddition, aluminum triisopropylate may be used as as catalyst. The moleratio of compound defined according to the structure: ##STR25## to alkylacetate is between 1:1 and 1:2 with a preferred mole ratio of a compoundhaving the structure: ##STR26## to alkyl acetate of about 1:1.5. Themole ratio of alkali metal alkoxide or aluminum isopropylate to thecompound having the structure: ##STR27## is between 0.5:1 and 1:0.5 witha preferred mole ratio of alkali metal alkoxide or aluminumtriisopropylate to the compound having the structure: ##STR28## isbetween 0.5:1 and 1:0.5 with a preferred mole ratio of alkali metalalkoxide or aluminum triisopropylate to the compound having thestructure: ##STR29## being about 1:1.

The compound having the structure: ##STR30## may be isolated and usedfor its organoleptic properties in augmenting or enhancing the aroma ofperfume compositions, colognes or perfumed articles or it may be used inthe subsequent reaction (ii) of this sequence.

In carrying out reaction (ii) of the sequence, to wit: ##STR31## themole ratio of diketone having the structure: ##STR32## to the allylhalide having the structure: ##STR33## is between 1:1 and 1:2 with apreferred mole ratio of about 1:1. In this reaction the allyl halidehaving the structure: ##STR34## is one wherein X is bromo or iodo.Actually allyl chloride can be used as a reactant but the allyl iodideor allyl bromide must be produced in situ. Accordingly, conveniently,allyl chloride may be used along with such materials as sodium iodide orsodium bromide whereby the allyl iodide or allyl bromide is produced insitu.

This reaction takes place at reflux conditions preferably at atemperature in the range of from about 60 up to about 80° C.) mostconveniently at atmospheric pressure. However, pressures greater than orless than atmospheric pressure may be used. Accordingly, the pressure ofreaction may vary from about 0.7 atmospheres up to about 10 atmospheresat reflux conditions. Higher temperatures of reaction give rise toshorter time periods of reaction. For example, when carrying out thereaction at 60°-70° C., the time of reaction is about 8 hours.

At the end of this reaction the reaction mass is purified by means ofsolvent stripping. The reaction product is then futher reacted by meansof reaction (iii) to wit: ##STR35## wherein M₁ is alkali metal such assodium, potassium and lithium and R₄ is lower alkyl such as methylethyl,1-propyl, 2-propyl, 1-methyl-2-propyl and 2-methyl, 2-propyl. In thealternative, a reaction can take place in the presence of aluminumtriisopropylate. The reaction preferably takes place in aqueoussolution. In place of the alkali metal alkoxide used or the aluminumtriisopropylate used, an aqueous alcoholic alkali metal hydroxidesolution can be used. Thus, for example, 1-liter of 50% aqueous sodiumhydroxide may be admixed with 500 ml of water and 500 ml methyl alcoholand the resulting mixture is then admixed with the compound having thestructure: ##STR36## This reaction is carried out at a temperature ofbetween 35° C. and 50° C.

The resulting product is then distilled from the reaction mass by meansof fractional distillation.

As an olfactory agent, the diketone of our invention having thestructure: ##STR37## (hereinafter referred to as "the diketone of ourinvention") can be formulated into or used as a component of a "perfumecomposition" or can be used as a component of a "perfumed article" orthe perfume composition may be added to perfumed articles.

The term "perfume composition" is used herein to mean a mixture oforganic compounds including, for example, alcohols, aldehydes, ketones(other than the diketone of our invention), nitriles, ethers, lactones,epoxides, natural essential oils, synthetic essential oils andhydrocarbons which are admixed so that the combined odors of theindividual components produce a pleasant or desired fragrance. Suchperfume compositions usually contain (a) the main note or the "bouquet"or foundation stone of the composition; (b) modifiers which round offand accompany the main note; (c) fixatives which include odoroussubstances which lend a particular note to the perfume throughout allstages of evaporation, and substances which retard evaporation and (d)topnotes which are usually low-boiling, fresh-smelling materials.

In perfume compositions, the individual component will contribute itsparticular olfactory characteristics, but the overall effect of theperfume composition will be the sum of the effects of each of theingredients and, in certain instances, a synergistic effect as a resultof the addition of certain ingredients. Thus, the individual compoundsof this invention, or mixtures thereof, can be used to alter the aromacharacteristics of a perfume composition, for example, by highlightingor moderating the olfactory reaction contributed by another ingredientin the composition.

The amount of the diketone of out invention which will be effective inperfume compositions depends on many factors, including the otheringredients, their amounts and the effects which are desired. It hasbeen found that perfume compositions containing as little as 0.05% ofthe diketone of this invention or even less can be used to impartinteresting, pineapple-like, oily, sweet, floral, fruity, woody,bark-like and green aromas with minty undertones to soaps, liquid orsolid anionic, cationic, nonionic or zwitterionic detergents, cosmetics,cosmetic powders, liquid or solid fabric softeners, drier-added fabricsoftener articles, (e.g., BOUNCE ®, a registered trademark of theProctor & Gamble Company of Cincinnati, Ohio), optical brightenercompositions, hypochlorite bleach compositions, fragranced polymers,hair conditioners and other products. The amount employed can range upto 70% or even higher and will depend on considerations of cost, natureof the end product and the effect desired on the finished product andparticular fragrance sought. Thus, for example, when fragrancing liquidbleach compositions containing alkali metal hypochlorite such as, forexample, sodium hypochlorite, for example CLOROX ® (registered trademarkof Clorox, Inc.), the amount employed can range as high as 100% of thefragrance involved in the liquid bleach. Indeed, a distinctive aspect ofour invention is the use of the diketone of our invention in a stableliquid bleach composition.

The diketone of our invention can be used alone or in a perfumecomposition as an olfactory component in detergents, soaps, spaceodorants and deodorants; perfumes; colognes, toilet waters; bath salts;hair preparations such as lacquers, brilliantines, pomades and shampoos;cosmetic preparations, such as creams, deodorants, hand lotions, sunscreens, powders such as talcs, dusting powders, face powders and thelike; liquid bleaches such as sodium hypochlorite-containing bleaches;floor waxes, automobile aromas and automobile polish compositions. Whenused as an olfactory component of a perfumed article as little as 0.01%of the diketone of our invention will suffice to impart an interestingpineapple-like, oily-sweet, floral, fruity, woody, bark-like and greenaroma with minty undertones. Generally no more than 1.5% is required toimpart such an aroma. However, in view of the rather low cost of thediketone of our invention up to 100% of the perfume composition can bethe diketone itself.

In summary, the range of the diketone of our invention in the perfumedarticle can be from 0.01% up to 1.5% or even higher.

In addition, the perfume composition can contain a vehicle or carrierfor the diketone along with other ingredients. The vehicle can be aliquid such as a non-toxic alcohol such as ethanol, a glycol such aspropylene glycol or the like. The carrier can be an adsorbent solid suchas a gum (e.g., guar gum or xanthan gum or gum arabic) or components forencapsulating the composition such as gelatin which can be used to forma capsule wall surrounding the perfume oil as by means of coacervationwith gelatin or by means of formation of a polymer around the perfumeoil as by polymerizing a urea formaldehyde prepolymer.

The following Example I serves to illustrate a method for carrying outthe process of our invention and producing intermediates useful in ourinvention. All parts and percentages given herein are by weight unlessotherwise specified.

EXAMPLE I PREPARATION OF 1(4-PENTENOYL)-3,3-DIMETHYLCYCLOHEXANE##STR38##

Into a 12-liter reaction flask equipped with stirrer, thermometer,condenser, "Y" tube, addition funnel, cooling bath, heating mantle,nitrogen blanket apparatus and gas bubbler is placed 2940 ml (30 moles)of ethyl acetate, 600 ml isopropyl alcohol, 1080 grams of sodiummethoxide (20 moles) and 150 grams (1 mole) of sodium iodide.

The reaction mass is cooled to 31°-32° C. and, over a period of twohours while maintaining the reaction temperature at 30°-32° C., 1540grams (7.4 moles) of 1-acetyl-3,3-dimethylcyclohexane is added to thereaction mass. After the addition of the1-acetyl-3,3-dimethylcyclohexane is complete, the reaction mass isstirred for a period of two hours while maintaining the temperature at27°-31° C.

The compound having the structure: ##STR39## may be isolated and usedfor its organoleptic properties as stated in Examples II, et seq. Thus,the compound having the structure: ##STR40## is distilled at 88°-93° C.at 3 mm/Hg pressure yielding a pineapple, oily, sweet, fruity, floral,woody, bark-like, and green aroma bearing material with mintyundertones.

Over a period of 15 minutes, 815 ml of allyl chloride is then added tothe reaction mass while maintaining the temperature at 30°-35° C. Thereaction mass is then refluxed at 60°-65° C. for a period of one hour.

At the end of the one hour period while maintaining the reaction mass at60°-62° C. an additional 815 ml (10 moles) of allyl chloride is added tothe reaction mass. The reaction mass is heated at 60°-62° C. over aperiod of eight hours.

The entire reaction mass is then transferred by vacuum to a 12 -literseparatory flask in a solution of 200 ml glacial acetic acid and 200 mlwater is added in order to bring the pH of the reaction mass to 6. Theresulting product is then washed with 4-liters of water and the aqueuslayer is separated. The organic phase is transferred back to a 12-literreaction flask which is fitted wth a "rushover" head. The contents arestripped at atmospheric pressure to a pot temperature of 100° C.3-Liters of material is collected.

A solution containing 1-liter of 50 percent sodium hydroxide, 500 mlwater and 500 ml methanol is produced.

1-Liter of the resulting alcholic sodium hydroxide solution is added tothe reaction mass at 41° C. (using cooling). The feed of the alcoholicsodium hydroxide solution to the reaction mass is over a 0.75 hourperiod. The temperature of the reaction mass is permitted to rise to 68°C. 500 Ml additional alcoholic sodium hydroxide solution is then addedto the reaction mass.

The contents of the reaction mass are then transferred back to theseparatory funnel and the aqueous layer is separated from the organicphase. The organic phase is acidified to a pH of 6 with 50 ml glacialacetic acid and then washed with 500 ml water. The organic phase is thendistilled in a 12" Goodloe column yielding the following fractions:

    ______________________________________                                               Vapor    Liquid   Vacuum         Weight                                Fraction                                                                             Temp.    Temp.    mm/Hg.  Reflux of                                    No.    (°C.)                                                                           (°C.)                                                                           Pressure                                                                              Ratio  Fraction                              ______________________________________                                         1     /56      /83      175.0   1:1    119.0                                  2     37       123      35.0    1:1    109.3                                  3     85       126      30.0    1:1    70.5                                   4     67       112      20.0    3:1    71.0                                   5     81       104      13.0    3:1    85.4                                   6     75       100      9.0     3:1    83.7                                   7     74        98      9.0     3:1    50.9                                   8     74       100      8.5     4:1    63.2                                   9     74       105      8.5     4:1    79.3                                  10     76       107      8.0     4:1    94.4                                  11     80       112      8.0     4:1    94.5                                  12     89       115      8.0     4:1    95.9                                  13     90       116      8.0     4:1    78.6                                  14     92       117      8.0     4:1    41.7                                  15     85       101      2.8     4:1    42.2                                  16     90       105      2.8     4:1    33.0                                  17     92       110      3.0     4:1    78.9                                  18     90       107      2.8     4:1    83.0                                  19     90       110      2.6     4:1    96.5                                  20     90       112      2.5     4:1    85.5                                  21     95       126      7.4     4:1    105.5                                 22     105      152      7.4     4:1    106.8                                 23     130      195      7.4     4:1    92.8                                  24     155      235      2.0     4:1    58.4                                  ______________________________________                                    

FIG. 1 is the GLC profile prior to distillation. (Conditions: 6'×0.25",12%, S.F.-96, column programmed at 80°-220° C. at 16° C. per minute.)The peak indicated by reference numeral 10 is the peak for the unreactedstarting material, the 1-acetyl-3,3-dimethylcyclohexane. The peakindicated by reference numeral "11" is the peak for the reaction productdefined according to the structure: ##STR41##

FIG. 2 is the GLC profile for Fraction 18 of the foregoing distillationproduct containing the compound having the structure: ##STR42## Thestructure of this compound is confirmed by means of MNR, IR and massspectral analyses.

EXAMPLE II SPICY-FLORAL FRAGRANCE

The following spicy-floral fragrance is prepared:

    ______________________________________                                        Ingredients         Parts by Weight                                           ______________________________________                                        Coumarin            6.0                                                       Musk Ambrette       8.0                                                       Benzyl Salicylate   12.0                                                      Bergamot Oil        6.0                                                       Hydroxycitronellal  5.0                                                       Lavandin Abriolis   4.0                                                       Patchouli Oil Light 1.0                                                       Phenyl Ethyl Alcohol                                                                              6.0                                                       Gamma Methyl Ionone 1.0                                                       Vetivert Oil, Bourbon                                                                             8.0                                                       Benzyl Acetate      14.0                                                      Linalool            8.0                                                       Amyl Cinnamic Aldehyde                                                                            10.0                                                      Indole (10% in diethyl phthalate)                                                                 1.0                                                       Eugenol             2.0                                                       The diketone produced                                                                             8.0                                                       according to Example I                                                        having the structure:                                                          ##STR43##                                                                    The diketone having the structure:                                             ##STR44##                                                                    adds to the spicy-floral fragrance an interesting pineapple, oily sweet,     fruity, woody, bark-like, green and minty profile of nuances. Thus, the     formulation can be described as "spicy and floral with oily sweet, fruity,     woody, bark-like, green and minty nuances".

EXAMPLE III PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill 100 grams oftalcum powder with 0.25 grams of a perfume substance as set forth inTable I below. The resulting powder has an excellent aroma as set forthin Table I below:

                  TABLE I                                                         ______________________________________                                        Perfume Substance                                                                              Aroma Description                                            ______________________________________                                        Diketone produced                                                                              A pineapple-like, oily sweet,                                according to     floral, fruity, woody,                                       Example I having bark-like and green aroma                                    the structure:   profile with minty under-                                     ##STR45##       tones.                                                       Perfume composition                                                                            Spicy and floral with oily                                   of Example II    sweet, fruity, woody, bark-                                                   like, green and minty nuances.                               ______________________________________                                    

EXAMPLE IV PERFUME LIQUID DETERGENT

Concentrated liquid detergent (lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818, issuedon Apr. 6, 1976, the specification of which is incorporated herein byreference) with aroma nuances as set forth in Table I of Example IIIsupra are prepared containing 0.10%, 0.15%, 0.20%, 0.25%, 0.30% and0.35% of the substances as set forth in Table I of Example III supra.They are prepared by adding and homogeneously mixing the appropriatequantity of fragrance formulation of Table I of Example III supra in theliquid detergents. The detergents all possess excellent aromas, theintensity increasing with greater concentration of the perfume substanceof Table I of Example III.

EXAMPLE V PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The perfume substances as set forth in Table I of Example III supra areincorporated into colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%,4.0%, 4.5% and 5.0% in 75%, 80%, 85% and 90% aqueous food grade ethanol;and into handkerchief perfumes at concentrations of 15%, 20%, 25% and30% (in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions).Distinctive and definitive aroma nuances as set forth in Table I ofExample III are imparted to the colognes and to the handkerchiefperfumes at all levels indicated above.

EXAMPLE VI PREPARATION OF SOAP COMPOSITIONS

One hundred grams of soap chips (IVORY®, produced by the Procter &Gamble Company of Cincinnati, Ohio) are mixed with 1 gram of each of theperfumery substances of Table I of Example III, supra until homogeneouscompositions are obtained. In each of the cases, the homogeneouscompositions are heated under 3 atmospheres pressure at 180° C. for aperiod of three hours and the resulting liquids are placed into soapmolds. The resulting soap cakes, on cooling, manifest excellent aromasas set forth in Table I of Example III supra.

EXAMPLE VII PREPARATION OF SOLID DETERGENT COMPOSITIONS

A detergent is prepared from the following ingredients according toExample I of Canadian Patent No. 1,007,948, (the specification for whichis incorporated herein by reference):

    ______________________________________                                        Ingredient          Percent by Weight                                         ______________________________________                                        Neodol ® 45-11 (a C.sub.14 -C.sub.15                                                          12                                                        alcohol ethoxylated with                                                      11 moles of ethylene oxide)                                                   Sodium carbonate    55                                                        Sodium citrate      20                                                        Sodium sulfate, water brighteners                                                                 q.s.                                                      ______________________________________                                    

This detergent is phosphate-free detergent. A total of 100 grams of saiddetergent is admixed with 0.10, 0.15, 0.20 and 0.25 grams of thesubstances of Table I of Example III supra. The detergent samples ineach case have excellent aromas as set forth in Table I of Example IIIsupra.

EXAMPLE VIII

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396, (the disclosure of which is incorporated by reference herein)a nonwoven cloth substrate useful as a drier-added fabric softeningarticle of manufacture is prepared wherein the substrate, the substratecoating and the outer coating and the perfuming material are as follows:

1. A water dissolvable paper ("Dissolvo Paper");

2. Adogen 448 (melting point about 140° F.) as the substrate coating;and

3. An outer coating having the following formulation (melting pointabout 150° F.):

57% C₂₀₋₂₂ HAPS

22% isopropyl alcohol

20% antistatic agent

1% of one of the perfume substances of Table I of Example III, supra.

Fabric softening compositions having aromas as set forth in Table I ofExample III are prepared which essentially consist of a substrate havinga weight of about 3 grams per 100 square inches; a substrate coatinghaving a weight of about 1.85 grams per 100 grams of substrate; and anouter coating having a weight of about 1.4 grams per 100 square inchesof substrate, thereby providing a total aromatized substrate and outercoating weight ratio of about 1:1 by weight of the substrate. The aromasas set forth in Table I of Example III are imparted in a pleasant mannerto the head space in the drier on operation thereof using each of thedrier-added fabric softening nonwoven fabric samples.

In the following examples, Aromox® DMC-W and Aromox® DMMC-W are 30%aqueous solutions of dimethyl cocoamine oxide; and Aromox® NCMDW is a40% aqueous solution of N-cocomorpholine oxide produced by ArmacDivision of ADZO of Chicago, Illinois.

EXAMPLE IX

Four drops of one or more of the perfume substances as set forth inTable I of Example III supra is added to 2 grams of Aromox ® DMC-W toproduce a clear premix. The clear premix is added to 200 grams of CLOROX® with stirring resulting in a clear, stable, single phase solution.Sufficient 1M aqueous NaOH is added to bring the pH of the mixture up to12.8. The solution remains substantially stable at 120° F. for a periodof 7 days. When the 5% aqueous sodium hypochlorite solution is used as alaundry bleach, the resulting laundry on dry-out in an atmosphere of 65%relative humidity yields substantially no characteristic "hypochlorite"odor but does have a faint, pleasant aroma as set forth in Table I ofExample III supra. Furthermore, no such characteristic "hypochlorite"aroma is retained on the hands of the individual handling such laundryin both the wet and the dry states.

EXAMPLE X

Aromox ® DMMC-W in various quantities is mixed with 0.1 grams of each ofthe substances of Table I of Example III supra. The resulting premixesare then added to 200 grams of an aqueous 5% sodium hypochloritesolution. Sufficient 12.5M aqueous NaOH is added to bring the pH of eachof the mixtures up to 13. The following results are obtained:

    ______________________________________                                        Percentage Aromox ®                                                                        Clarity of hypochlorite solu-                                DMMC-W           tion after addition of premix                                ______________________________________                                        0.23%            Clear after three days                                       0.15%            Clear after three days                                       0.08%            Initially slightly turbid;                                                    two phases exist after                                                        three days                                                   ______________________________________                                    

When the 5% aqueous sodium hypochlorite solutions are used as laundrybleaches, the resulting laundry batches on dry-out in an atmosphere of65% relative humidity yields substantially no characteristic"hypochlorite" odor but do have faint, pleasant aromas as set forth inTable I of Example III supra. Furthermore, no such characteristic"hypochlorite" aroma is retained on the hands of the individual handlingsuch laundry batches in both the wet and the dry states.

EXAMPLE XI

Two grams of Aromox ® DMMC-W are admixed with eight drops of each of theperfume substances of Table I of Example III supra. Each of the premixesis then added with stirring to 200 grams of a 7% aqueous solution oflithium hypochlorite. Sufficient 3M aqueous LiOH is added to bring thepH of the solution to 13.4. The mixtures are then heated to 120° F. andmaintained at that temperature with stirring for a period of one week.The resulting solution remains clear in a single phase. When used aslaundry bleaches, the resulting bleached laundry batches on dry-out inan atmosphere of 50% relative humidity retain an aroma as described inTable I of Example III whereas without the use of the substances ofTable I of Example III, the bleached laundry batches have faintcharacteristic disagreeable "hypochlorite" aromas.

EXAMPLE XII

Two grams of Aromox ®DMMC-W are admixed with eight drops of each of thesubstances of Table I of Example III supra. The premixes are then addedwith stirring to 200 grams of a mixture containing 4.5% aqueous sodiumhypochlorite and 4.5% aqueous lithium hypochlorite. Sufficient 4Maqueous LiOH is added to bring the pH of the solutions to 13.4. Themixtures are then heated to 120° F. and maintained at that temperaturefor a period of one week. The resulting solutions remain clear in asingle phase. When used as laundry bleach, the resulting bleachedlaundry batches on dry-out in an atmosphere of 50% relative humidityretain an aroma as set forth in Table I of Example III supra whereaswithout the use of the perfume substances as set forth in Table I ofExample III supra, the bleached laundry batches have faintcharacteristic and disagreeable "hypochlorite" aromas.

EXAMPLE XIII

Two grams of Aromox ®DMMC-W are admixed with eight drops of one of theperfume substances of Table I of Example III supra. These premixes arethen added with stirring to 200 grams of mixture containing 4% aqueoussodium hypochlorite and 4% aqueous lithium hypochlorite. Sufficient 2Maqueous NaOH is added to bring the pH of the solutions to 13.4. Themixtures are then heated to 110° F. and maintained at that temperaturewith stirring for a period of two weeks. The resulting solutions remainclear as a single phase when used as laundry bleaches. The resultingbleached laundry batches on dry-out in an atmosphere of 50% relativehumidity retain aromas as set forth in Table I of Example III suprawhereas without the use of the perfume substances of Table I of ExampleIII supra, the bleached laundry batches have faint, characteristicdisagreeable "hypochlorite" aromas.

EXAMPLE XIV

Four drops of each of the substances of Table I of Example III supra areadded to 1.5 grams of Aromox ®NCMDW to produce a clear premix. The clearpremixes are added to 200 grams in each case of CLOROX ® with stirringresulting in a clear single phase solution. Sufficient 1M aqueous NaOHis added to bring the pH of the mixture up to 12.8. The solution remainssubstantially stable at 120° F. for a period of 7 days. When the 5%aqueous sodium hypochlorite solution is used as a laundry bleach, theresulting laundry on dry-out in an atmosphere of 65% relative humidityyields substantially no characteristic hypochlorite aroma but does havea faint pleasant aroma as set forth in Table I of Example III supra.Furthermore, no such characteristic "hypochlorite" aroma is retained onthe hands of the individual handling such laundry in both the wet andthe dry states.

EXAMPLE XV

Four drops of each of the substances of Table I of Example III supra areadded to 1 gram of n-undecyl dimethyl amine oxide to produce a clearpremix in each case. The clear premix is added to 200 grams of CLOROX ®with stirring resulting in a clear, single phase solution. Sufficient 1Maqueous NaOH is added to bring the pH of the mixture to 12.8. Thesolution remains substantially stable at 120° F. for a period of 7 days.When the 5% aqueous sodium hypochlorite solution is used as a laundrybleach, the resulting laundry on dry-out in an atmosphere of 65%relative humidity yields substantially no characteristic hypochloriteodor but does have a faint pleasant odor as set forth in Table I ofExample III supra. Furthermore, no such characteristic "hypochlorite"odor is retained on the hands of the individual handling such laundry inboth the wet and the dry states.

EXAMPLE XVI

Four drops of each of the substances of Table I of Example III supra isadded to 1 gram of n-dodecyl dimethyl amine oxide to produce a clearpremix. The clear premix is added to 200 grams of CLOROX ® with stirringresulting in a clear stable single phase solution. Sufficient 1M aqueousNaOH is added to bring the pH of the mixture up to 12.8. The solutionremains substantially stable at 120° F. for a period of 7 days. When the5% aqueous sodium hypochlorite solution is used as a laundry bleach, theresulting laundry on dry-out in an atmosphere of 65% relative humidityyields substantially no characteristic "hypochlorite" odor but does havea faint pleasant aroma as set forth in Table I of Example III supra.Furthermore, no such characteristic "hypochlorite" aroma is retained onthe hands of the individual handling such laundry in both the wet andthe dry states.

EXAMPLE XVII

One gram of n-tridecyl dimethyl amine oxide is admixed with eight dropsof each of the substances of Table I of Example III supra. Each of thepremixes is then, with stirring, added to 200 grams of a 7% aqueoussolution of lithium hypochlorite. Sufficient 3M aqueous LiOH is added tobring the pH of the solution to 13.4. The mixture is then heated to 120°F. and maintained at that temperature with stirring for a period of oneweek. The resulting solution remains clear in a single phase. When usedas a laundry bleach, the resulting bleached laundry on dry-out in anatmosphere of 50% relative humidity retains an aroma as set forth inTable I of Example III supra; whereas without the use of any of thesubstances of Table I of Example III supra, the bleached laundry has afaint, characteristic, disagreeable "hypochlorite" aroma.

What is claimed is:
 1. A process for preparing the compound definedaccording to the structure: ##STR46## comprising the steps of: (i)reacting an alkyl acetate having the structure: ##STR47## with1-acetyl-3,3-dimethylcyclohexane having the structure; ##STR48## whereinR₂ is C₁ -C₅ alkyl thereby forming a diketone having the structure:##STR49## at a temperature of from about 20° C. up to about 50° C. and apressure of from about 0.7 atmospheres up to about 5 atmospheres in thepresence of an alkali metal alkoxide catalyst or aluminum isopropylatecatalyst, the mole ratio of said 1-acetyl-3,3-dimethylcyclohexane:alkylacetate being between 1:1 and 1:2 and the mole ratio of alkali metalalkoxide or aluminum triisopropylate:1-acetyl-3,3-dimethylcylcohexanebeing between 0.5:1 and 1:0.5;(ii) reacting the diketone having thestructure: ##STR50## with the allyl halide having the structure:##STR51## wherein X is bromo or iodo therby forming the compound definedaccording to the structure: ##STR52## under reflux conditions at apressure of from about 0.7 atmospheres up to about 10 atmospheres, themole ratio of diketone:allyl halide being from 1:1 up to 1:2; (iii)performing a retro-Claisen reaction on the allyl diketone having thestructure: ##STR53## in order to form the compound having the structure:##STR54## by means of reacting the compound having the structure:##STR55## with an alkali metal alkoxide or aluminum triisopropylate orin an aqueous alcoholic solution at a temperature of between 35° C. and50° C.; and (iv) isolating the compound having the structure: ##STR56##from the reaction mass.
 2. The process of claim 1 wherein the step (iv)of isolating the compound having the structure: ##STR57## is by means offractional distillation.